Sodium Azide → HCID 86650249, compound

HRID 221666Notes

Reaction equation

[C:1]([O:5][C:6](=[O:22])[NH:7][C:8]1[CH2:9][O:10][CH2:11][C:12]([C:15]2[CH:20]=[CH:19][CH:18]=[C:17](Br)[CH:16]=2)([CH3:14])[N:13]=1)([CH3:4])([CH3:3])[CH3:2].[N-:23]=[N+:24]=[N-:25].[Na+].O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+].CN[C@@H]1CCCC[C@H]1NC>C(O)C.O.[Cu](I)I>[C:1]([O:5][C:6](=[O:22])[NH:7][C:8]1[CH2:9][O:10][CH2:11][C:12]([C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([N:23]=[N+:24]=[N-:25])[CH:16]=2)([CH3:14])[N:13]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 90 °C

Procedure

[5-(3-Bromo-phenyl)-5-methyl-5,6-dihydro-2H-[1,4]oxazin-3-yl]-carbamic acid tert-butyl ester (5.03 g, 12.67 mmol), sodium azide (1.647 g, 25.3 mmol), sodium ascorbate (0.125 g, 0.63 mmol), copper iodide (0.241 g, 1.27 mmol) and (1R,2R)-N,N′-dimethyl-cyclohexane-1,2-diamine (0.270 g, 1.90 mmol) were dissolved in ethanol (17.7 ml) and water (7.6 ml). The mixture was stirred under N2 at 90° C. for 4 h and then poured into 1M aqueous KHCO3 solution. The mixture was extracted with EtOAc, and the organic phase was washed with brine, dried with Na2SO4 and evaporated under reduced pressure. The residue was purified by chromatography on silica gel (cyclohexane/EtOAc=7:3) to yield the title compound. 1H-NMR (500 MHz, DMSO-d6): 9.57 (br, 1H), 7.38 (m, 1H), 7.24 (d, 1H), 7.18 (br, 1H), 7.0 (br, 1H), 4.50-4.30 (m, 2H), 3.75-3.35 (m, 2H), 1.41 (s, 9H), 1.36 (s, 3H); MS: 332 [(M+H)+].

Workup

extractionThe mixture was extracted with EtOAc
washthe organic phase was washed with brine
dry with materialdried with Na2SO4
customevaporated under reduced pressure
customThe residue was purified by chromatography on silica gel (cyclohexane/EtOAc=7:3)

Sources & evidence

ORD record: ord-cf30f2dcfdbd4cc5bace09c50373a8d0
Source dataset: uspto-grants-2012_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08207164B2

Reaction notes

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